Bromoalkyl-(di)-thiolphosphoric acid esters

ABSTRACT

BROMOALKLY-(DI)-THIOLPHOSPHORIC ACID ESTERS, I.E. O-((2BROMO-OPTIONALLY 1 AND/OR 2-ALKYL AND/OR CHLORALKYL)ETHYL AND (3-BROMO-OPTIONALLY 1,2 AND/OR 3-ALKYL AND/OR CHLOROALKYL)-PROPYL)-S-(AKYL, CHLOROALKYL, PHENYL, CHLOROPHENYL AND ALKYLPHENYL)-(S-S-ALKYL, ALKYLMERCAPTOALKYL, PHENYL, CHLOROPHENYL AND ALKYLPHENY1) AND O-(ALKYL AND CYCLOALKYL) )-THIOL- AND -DITHIOL-PHOSPHORIC ACID ESTERS OF THE FORMULA   BR-C(-R1)(-R2)-(C(-R3)(-R4)N-C(-R5)(-R6)-O-P(=O)(-Y-R8)   -S-R7   IN WHICH R1 TO R6 EACH INDIVIDUALLY, IS HYDROGEN, ALKYL OF 1-2 CARBON ATOMS, OR CHLOROALKYL OF 1-2 CARBON ATOMS, R7 IS ALKYL OF 1-4 CARBON ATOMS, CHLORO ATOMS, CHLOROSUBSTITUTED ALKYL OF 1-2 CARBON ATOMS, PHENYL, CHLOROPHENYL, OR ALKYLPHENYL HAVING 1-4 CARBON ATOMS IN THE CORRESPONDING ALKYL MOIETY. Y IS OXYGEN OR SULFUR, R8 IS, WHEN Y IS SULFUL, ALKYL F 1-4 CARBON ATOMS, ALKYLMERCAPTO-ALKYL HAVING 1-4 CARBON ATOMS IN THE ALKYLMERCAPTO MOIETY AND 1-4 CARBON ATOMS IN THE ALKYL MOIETY, PHENYL, CHLOROPHENYL, OR ALKYLPHENYL HAVING 1-4 CARBON ATOMS IN THE CORRESPONDING ALKYL MOIETY WHEREAS R8 IS, WHEN Y IS OXYGEN, ALKYL F 1-4 CARBON ATOMS OR CYCLOALKYL OF 5-6 RING CARBON ATOMS, AND N IS O OR 1, WHICH POSSESS FUNGICIDAL, BACTERICIDAL, AND ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES.

United States Patent US. Cl. 260-964 15 Claims ABSTRACT OF THE DISCLOSURE Bromoalkyl-(di)-thiolphosphoric acid esters, i.e. O-[(2- bromo-optionally 1 and/or 2-alkyl and/or chloroalkyl)- ethyl and (3-bromo-optionally 1,2 and/or 3-alkyl and/or chloroalkyl)-propyl]-S-[akyl, chloroalkyl, phenyl, chlorophenyl and alkylphenyl]-[S-(alkyl, alkylmercaptoalkyl, phenyl, chlorophenyl and alkylphenyl) and O-(alkyl and cycloalkyl)]-thioland -dithiol-phosphoric acid esters of R to R each individually, is hydrogen, alkyl of 1-2 carbon atoms, or chloroalkyl of 1-2 carbon atoms, R; is alkyl of 1-4 carbon atoms, chloro atoms, chlorosubstituted alkyl of 12 carbon atoms, phenyl, chlorophenyl, or alkylphenyl having 1-4 carbon atoms in the corresponding alkyl moiety,

Y is oxygen or sulfur,

R is, when Y is sulfur, alkyl of l4 carbon atoms, alkylmercapto-alkyl having l-4 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl moiety, phenyl, chlorophenyl, or alkylphenyl having 1-4 carbon atoms in the corresponding alkyl moiety whereas R is, when Y is oxygen, alkyl of 1-4 carbon atoms or cycloalkyl of -6 ring carbon atoms, and

n is 0 or 1,

which possess fungicidal, bactericidal, and arthropodicidal, especially acaricidal and insecticidal, properties.

The present invention relates to and has for its objects the provision for particular new bromoalkyl-(di)-thiolphosphoric acid esters, i.e. O-[(2-bromo-optionally 1 and/ or 2-alkyl and/ or chloroalkyl)-ethyl and (3-bromo-optionally l, 2 and/or 3-alkyl and/or chloroalkyl)-propyl]-S- [alkyl, chloroalkyl, phenyl, chlorophenyl and alkylphenyl]-[S-(alkyl, alkylmercaptoalkyl, phenyl, chlorophenyl and alkylphenyl) and O-(alkyl and cycloalkyl) ]-thioland -dithiol-phosphoric acid esters, which possess fungicidal, bactericidal, and arthropodicidal, especially insecticidal and acaricidal, properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. fungi, bacteria and arthropods, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

In US. Pat. 2,690,450, thiolphosphoric acid aryl esters are described which possess parastiticidal, in particular insecticidal, but also fungicidal, properties. From this U8.

Patent, however, it can be learned only that the above- 3,641,224 Patented Feb. 8, 1972 "ice mentioned compounds are suitable as specific fungicides for the control of brown rot (Sclerotinia fructicola) and early blight (Alternaria solani). There is no indication in said US. Pat. 2,690,450 as to whether the products disclosed therein also possess a practical effectiveness against fungal pathogenic agents on rice plants, particularly against the fungus Piricularia oryzae.

It has been found, in accordance with the present invention, that the particular new bromoalkyl-(di)-thiolphosphoric acid esters of the formula R to R each individually, is hydrogen, alkyl of 1-2 carbon atoms, or chloroalkyl of 1-2 carbon atoms,

R, is alkyl of 1-4 carbon atoms, chloro-substituted alkyl of 1-2 carbon atoms, phenyl, chlorophenyl, or alkylphenyl having 1-4 carbon atoms in the corresponding alkyl moiety,

Y is oxygen or sulfur,

R is, when Y is sulfur, alkyl of 1-4 carbon atoms, alkylmercapto-alkyl having l-4 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl moiety, phenyl, chlorophenyl, or alkylphenyl having 14 carbon atoms in the corresponding alkyl moiety whereas R is, when Y is oxygen, alkyl of 1-4 carbon atoms or cycloalkyl of 5-6 ring carbon atoms, and

n is 0 r l,

with the provision that at least one of R and R is phenyl,

chlorophenyl or alkylphenyl,

in which exhibit strong fungicidal, bactericidal and arthropodicidal, especially insecticidal and acaricidal, properties.

It has been furthermore found, in accordancewith the present invention, that the compounds of Formula I above may be produced by a process which comprises reacting a bromoalkyl-S-alkylor -phenyl-thiolphosphoric acid diester chloride of the formula in which Y and R are the same as defined above, or a salt thereof.

Advantageously, the particular new compounds of Formula I above are distinguished by outstanding fungitoxic properties, in particular against fungal pathogenic agents on rice plants. Surprisingly, the instant compounds are in this respect clearly superior to comparable known active compounds of analogous constitution which have already been proposed for the same purpose. In addition, the in stant compounds also possess effective bactericidah insecticidal and acaricidal activity, coupled with low toxicity to Warm-blooded creatures and concomitantly 'low'phytotoxicity to higher plants. The new compounds of the present' invention therefore represent a genuine enrichment of the art.

If, for example, 0-(2-bromoethyl)-S-(methyl)-thiol-' phosphoric acid diester chloride and thiophenol are used as starting materials, the course of the production process according to the present invention can be illustrated by the following reaction scheme:

ll Br-CHz-CHz-O-F-S-Q S CH Advantageously, in accordance with the present invention, in the various formulae herein: R to R each individually, represents hydrogen; lower alkyl hydrocarbon of 1-2 carbon atoms such as methyl and ethyl, i.e. C alkyl, especially methyl;

or chloro-substituted lower alkyl hydrocarbon of l-2 carbon atoms such as chloromethyl, 2-chloro-ethyl and l-chloro -ethyl, i.e. chloro-C alkyl, especially chloromethyl; R represents lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.butyl, and the like, i.e. C alkyl, especially C1-2 y chloro-substituted lower alkyl of 1-2 carbon atoms as defined above, i.e. chloro-C alkyl, especially 2- chloroethyl; phenyl; chlorophenyl such as 2-, 3- and 4-chlorophenyl, es-

pecially 2- and 4-chlorophenyl; or lower alkyl phenyl having 1-4 carbon atoms in the alkyl moiety such as 2-, 3- and 4-methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.-butyl-phenyl, i.e. 2-, 3- and 4-C alkyl phenyl, especially 2- and 4-C or C alkyl phenyl, and more especially 2- and 4-methyl phenyl; Yrepresents oxygen; or sulfur; R represents, when Y is sulfur,

lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl to tart-butyl inclusive, andthe like, as defined above, i.e. C alkyl, especially C alkyl; lower alkyl hydrocarbon mercapto-substituted lower alkyl hydrocarbon having 14 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl hydrocarbon moiety such as methyl, ethyl, nand iso-propyl, n-, iso-, secand tert.-butyl, and the like, -mercapto-methyl to tert.-buty1 inclusive, as defined above, and the like, i.e. C alkylmercapto- C alkyl, especially C alkylmercapto-C alkyl, and more especially ethylmercapto-ethyl; phenyl; chlorophenyl as defined above, especially 2- and 4- chlorophenyl; or lower alkyl phenyl having 14 canbon atoms in the alkyl moiety such as 2-, 3- and 4-methyl to tert.- butyl inclusive, and the like, -phenyl, i.e. 2-, 3- and 4-C alkyl phenyl, especially 2- and 4-C r C alkyl phenyl, and more especially 2- and 4-methyl phenyl; whereas R represents, when Y is oxygen,

lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl to tert.-butyl inclusive as defined above, and the like, i.e. C alkyl, especially C alkyl; or cycloallcyl hydrocarbon of 5-6 ring carbon atoms such as cyclopentyl, cyclohexyl, and the like, i.e. C cycloalkyl, especially cyclohexyl; and n represents a whole number from 0 to 1, preferably 0; with the proviso that at least one of R and R is such phenyl, chlorophenyl or alkyl phenyl, i.e. -R-, will be such phenyl, chlorophenyl or alkyl phenyl when Y is oxygen, and R or R or both will be such phenyl, chlorophenyl or alkylphenyl when Y is sulfur.

In particular, R is hydrogen, or C alkyl, especially methyl; R to R and R are hydrogen; R is hydrogen, or C alkyl, especially methyl, or ch1oro-C alkyl, especially chloromethyl; R is C or C alkyl, or chloro-C alkyl, especially 2-chloroethyl, or phenyl, or chloro-phenyl, especially 2- and 4-chloropheny1, or C alkyl-phenyl, especially methylphenyl, more especially 2- and 4-C alkyl-phenyl, and particularly 2- and 4-methylphenyl; Y is oxygen or sulfur; R is, when 'Y is sulfur, C or C alkyl, or C alkylmercapto-C alkyl, especially C alkylmercapto-C alkyl, or phenyl, or chlorophenyl, especially 2- and 4-chlorophenyl, or C alkyl-phenyl, especially methylphenyl, more especially 2- and 4-C alkyl-phenyl, and particularly 2- and 4-methylphenyl; whereas R is, when Y is oxygen, C alkyl, especially C alkyl, or C cycloalkyl, especially cyclohex l.

iP ieferably, R is C alkyl, chloro-C alkyl, phenyl or chlorophenyl; and R is, when Y is sulfur, C alkylmercapto-C alkyl, phenyl, chlorophenyl or C alkyl phenyl, whereas R is, when Y is oxygen, C alkyl or C cycloalkyl. I

The type of starting alcohols, mercaptans and throphenols usable in accordance with the process of the present invention are clearly characterized by Formula III above.

These starting compounds are well known and can be prepared on an industrial scale.

The types of starting bromoalkyl-S-alkylor -phenylthiolphosphoric acid diester chlorides usable in accordance with the process of the present invention are clearly characterized by Formula II above.

Examples of such starting bromo-alkyl-S-alkylor -phenyl-thiolphosphoric acid diester chlorides which can be reacted according to the present invention are:

O-(2-bromo-ethyl-S-methylor S-phenyl,

O-(2-bromo-ethyl)-S-(4-methyl-phenyl)- O-(2-bromo-ethyl)-S-(4'-chloro-phenyl)-,

0- 3-bromo-butyl- (2) ]-S-phenyl-,

0- 3-bromo-butyl-( 1) ]-S-methylor S- (4-methyl- O-[1,1-dichloro-3-bromo-propyl (2) ]-S- (4-chloro- O- [3-bromo-butyl- (2) -S-methylor S-phenyl-,

0- l-bromo-propyl 2) 1 -S-methylor S-phenyl-,

O- l-bromo-propyl- 2) -S-ethylor S-( 3 -chloroand the like, -thiolphosphoric acid diseaster chlorides.

The bromoalkyl-S-alkylor -phenyl thiolphosphoric acid diester chlorides of Formula II above usable as starting materials are not yet known from the literature. It has been found that the bromo-alkyl-S-alkylor phenylthiolphosphoric acid diester chlorides concerned are obtained with very good yields as well as in outstanding purity by precursor reaction of equimolar amounts of 2-chloro-phospholanes or 2-chloro-phosphorinanes of the formula with aliphatic or aromatic sulfenic acid bromides of the formula R --SBr v) In the aforesaid Formulae IV and V, R to R and n are the same as defined above.

The precursor reaction can be carried out in the presence or absence of solvents or diluents such as (optionally chlorinated) aliphatic and aromatic hydrocarbons, ethers or low-molecular-weight ketones and nitriles; and the like, at temperatures of substantially between about 20 to +50, preferably at between about 10 to +30 C.

It is preferable to add the sulfenic acid bromide (possibly diluted with one of the above-mentioned solvents) dropwise to the solution or suspension of the phospholane or phosphorinane derivative at a temperature within the above-mentioned range with stirring and possible cooling of the reaction mixture. After completion of the addition, the mixture is left to stand for about 1 to 3 hours to complete the reaction, the solvent is then drawn off and the residue may be subjected to fractional distillation under reduced pressure. In most cases, however, with the described method of working, the starting materials are obtained in such high purity that their further reaction is possible without purification.

According to a particular embodiment of the process of the present invention, isolation of the bromoalkyl-S- alkylor -phenyl-thiolphosphoric acid diester chlorides concerned is dispensed with entirely and, instead, the reaction products of the above-mentioned 2-chloro-phospholanes or -phosphorinanes with the appropriate sulfenic acid bromides are immediately reacted in a one-pot process with the required alcohol, mercaptan or thiophenol of Formula III above.

The process according to the present invention can also be carried out in the presence of solvent or diluents. As such, practically all inert organic solvents are suitable. Particularly good results, however, have been obtained with (optionally chlorinated) aliphatic and aromatic hydrocarbons, such as methylene chloride, dichloroethane, di-, triand tetrachloroethylene, chloroform, carbon tetrachloride, benzine, benzene, chlorobenzene, toluene and xylene; ethers, for example diethyl and di-n-butyl ether, dioxan, tetrahydrofuran or low-molecular-weight aliphatic ketones or nitriles, for example acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone, acetonitrile and propionitrile; and the like.

Furthermore, the alcohols, mercaptans and thiophenols to be reacted according to the present process can be reacted in the form of their salts, preferably the appropriate alkali metal or ammonium salts. It is alternatively possible to work the process in the presence of acid-binding agents. As the latter, the usual acid acceptors are suitable, such as alkali metal carbonates, alcoholates and hydroxides, for example potassium and sodium carbonate, methylate, ethylate and hydroxide, as well as tertiary aliphatic, aromatic or heterocyclic bases, such as triethylamine, dimethylaniline, benzyldimethylamine or pyridine; and the like.

The reaction temperatures in the case of the process according to the present invention can be varied within a fairly wide range. In general, the reaction is carried out at substantially between about -100 C. (or the boiling point of the mixture), preferably at between about 80 C.

For the carrying out of the instant process there is theoretically necessary-as can be seen from the above reaction equation-1 mol of alcohol, mercaptan or thiophenol per mol of bromoalkyl-S-alkylor phenyl-thiophosphoric acid diester chloride. Usually, equimolar amounts of the starting materials are employed, but an excess of the second reaction'component can sometimes be advantageous. It has proved expedient either to add dropwise, with stirring, the 'bromoalkyl-S-alkylor -phenyl- 6 thiolphosphoric acid diester chloride to the solution or suspension of the alcohol, mercaptan or thiophenol in one of the above-mentioned solvents or, conversely, to add the appropriate hydroxylor sulfohydryl-group-containing compound of Formula III above to the diester chloride (or to the reaction product of the appropriate 2-chloro phospholane or -phosphorinane derivative with the particular sulfenic acid bromide).

After mixing the starting components, the reaction mixture is, in order to complete the reaction, left to stand for some time (for example 1 to 3 hours) and/or heated at the above-mentioned temperatures until the reaction is complete, for example for several hours (or overnight), with stirring.

The working up of the mixture may take place, in known manner, by pouring the mixture into ice Water, optionally deacidifying the solution, taking up the separated reaction product (in most cases in oily form) in a water-immiscible solvent, preferably one of the abovementioned hydrocarbons, for example benzene, washing the organic layer until there is a neutral reaction, separation of the phases, drying of the solution, distilling olf the solvent and, if possible, fractional distillation of the residue under reduced pressure.

The instant compounds are obtained in most cases in the form of colorless to slightly yellow-colored viscous oils, some of which can be distilled under greatly reduced pressure without decomposition. When this is not possible, the compounds obtained can, for purification, be slightly distilled, that is freed from the last volatile impurities by longer heating to slightly to moderately elevated temperatures in a vacuum.

Surprisingly, the instant new compounds when compared to the closest active compounds of analogous constitution and the same type of activity previously known from the literature are distinguished by a substantially better bactericidal, insecticidal, acaricidal, but especially fungicidal, effectiveness, as well as a repellent effect against destructive birds, with only slight toxicity to warm-blooded animals and only slight phytotoxicity. The effect sets in rapidly and is long-lasting.

By reason of their above-mentioned properties, the instant new compounds can be used with success in plant protection endeavors, especially against a multiplicity of the most diverse plant and animal parasites, such as fungi, sucking and eating insects, Diptera and mites.

The instant new active compounds exhibit an especially strong fungitoxic activity against phytopathogenic fungi. Likewise, diseases caused by bacteria can be controlled with these compounds. The good compatibility with warmblooded animals and with higher plants permits the use of such compounds as plant protection agents against fungal diseases. In the concentrations necessary for the control of fungi, the instant compounds do not damage cultivated plants.

Fungitoxic agents in plant protection are used for the control of fungi from the most diverse classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The instant active compounds possess a broad spectrum of activity. They can be used against parasitic fungi on above-the-soil parts of plants, fungi which cause tracheomycosis, fungi which attack the plants from the soil and seed-borne as well as soil-inhabiting fungi.

The instant new compounds have given particularly good results in the control of rice diseases. Such compounds show an excellent activity against the fungi Piricularia oryzae and Pellicularia sasakii, by reason of which they may be used for the joint control of these two diseases. This represents a substantial advance in the art, since up to now agents of different chemical constitution were individually necessary to combat and control these two fungi, respectively. Surprisingly, the instant active compoundsshow not only a protective activity, but also a curative effect.

However, the instant new compounds also act against other fungi which infest rice or other cultivated plants, such as Cochliobolus miyabeanus, Mycosphaerella musicola, Cercosporw person ata, Botrytis cinema and Alternaria species, Fusarium species, Verticillium alboatrium and Phialophom cinerescens; and the like.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual pesticidal diluents or extenders, i.e. conventional pesticidal dispersible carrier vehicles such as solutions, emulsions, suspension,s emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticidal dispersible liquid diluent carriers and/r dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticidal surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), clorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistant, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/ or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicides, or bactericides, or herbicides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

-As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.-0001%, preferably 0.011%, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/ or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dis persing agent, and an amount of the active compound 8 which is effective for the purpose in question and which is generally between about 0.0001-%, and preferably 0.0195%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

In particular, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, bacteria or arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of fungi, bacteria, insects and acarids which comprises applying to at least one of correspondingly (a) such pests, i.e. fungi, bacteria, insects or acarids, and (b) the corresponding habitat, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. a fungicidally, bactericidally or arthropodicidally, especially insecticidally or acaricidally, effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, squirting, fumigating, incrustations, dressings, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention is illustrated without limitation by the following examples:

EXAMPLE 1 Piricularia test: liquid preparation of active compound Solvent: 4 parts by weight acetone Dispersing agent: 0.05 part by weight sodium oleate Other additive: 0.2 part by weight gelatin Water: 95.75 parts by 'weight The amount of the particular active compound required for the desired concentration of such active compound in the spray liquor is mixed with the stated amount of solvent, and the resulting concentrate is diluted with the stated amount of water containing the stated dispersive agent and other additive.

Test for protective action 30 rice plants about 14 days old are sprayed (i.e. treated) with the active compound-containing spray liquor until dripping wet. The plants remain in a greenhouse at temperatures of 22 to 24 C. and a relative atmospheric humidity of about 70% until the plants are dry. The plants are then inoculated with an aqueous sus-' pension of 100,000 to 200,000 spores/ml. of Piricularia oryzae and placed in a chamber at 24-26 C. and 100% relative atmospheric humidity.

5 days after inoculation, the infestation of all the leaves present at the time of inoculation is determined as a percentage of the untreated but also inoculated control plants. 0% means no infestation; 100% means that the infestation is exactly as great as in the case of the control plants.

The particular active con ipounds tested, their concentrations and the results'obt'ained can be seen from the following Table 1:

Test for curative action The above, testshows the protective efletof the a ctiv e *Pirtcuiariatest/iiquid reparation of active compound v v .-[Pr.=protectivee ect. Cu.r.=curative efiect] v i i Infestation as "Activelcomponnd.

new panama Infestation as a percentage of ,Vthe infestation of the un: treated control with a concentration ofactive c m u d (in percent) of0.05

, a rcent eoi' tliifiniestia tion of the un- 1: treat'edcontroi m: 'witha concentration of active compound (in percent) Active compound of0.05 (A)VL--' Tr. 25

0211 0 -SN0z (Comparative preparation known from U.S.'

Pat. 2,690,450.)

(12)--- BI-CHr-CHa-O 0 P1. 0 S

GH -0 a- CH," "tr. 0 (21).-. Br-CH2CH2O\O YBI CHE CH O 0 Our. 25

A 02115-8 .52 t, C2H5-0 W (3 BI-CH2-0H2-O 0 Pl; 0 (171); CHL H I Pr 0 5 C111. 50 C1 Br-CEh- 11-o 0 Br-om-om-o 0 Pr! 0 CKHFO/ (41)"; s

1s)1..- CH v Pr. 0 A} v Our. 25 45 Br-CH2 H-0 0 5, CH3 Pr: 0 \{L B1CH2CH2-O O 1 {l C1--CH,gCH'z- -S 191 EH5 l I". I Pr. 7 0 (69m 0 PL 0 Br-OHz- H-O\E Br cm cm-o t s 1 c1cH,-0ms w (1, BrCHzOHz-O\E Pr. 0 v (201)" CH8 CH3 PL I 8 SCi ;v BF 0 iL (8 OH Pr. 17 CH3"S BPCHPCHPOQfl (211).. CH8 CH5 Pr. 0 P-s- H v Cur. o 4/ Br- 11-0 o 1 i -e-Q-OH;

, (9 Br-CHaCH10\fi PI. 0 CHF'S 0113-0 Br-CHz-CHz- H0 0' v 101)-- BrcH,-cH,-o o Pr. 12 i 02115-0 (231)" OIUCII2 I Pr. 0 111 Br-cm-om0 Pr. 0 O 12 CgHg-O H v 111 v EXAMPLE 2 My zus test (contact action) li P 10 1 r r S b h e acetone J 1Tetranychus=test- Solvent: 3 parts by weight acetone Eniulsifierz 1 part by weight alkylarylpolyglycbh ether limulsifierxzll part by weight alkylaryl polyglycol ether 5 v r I I a e To produce a suitable preparation of the particular I o produce a suitable prep ration of the particular active compound, l-part by weight of such active pomactive compo und 1 part by weighttof-such active compound is mixed with the stated'ampunt of-s0lvent ;,cenpound is mixed with the stated amount of .solvent icontaining the stated amount of emulsifier and the resulting tain ing thestated amount oi emulsifier and the resulting concentrate is diluted with water to the desiredfinal onconcentrate is dilutedwitlrwaterto the desired finalconcentrat ion. A a 1;: centration V Beanplants. (phgseolus yulgaris),yyhich hayga height Cabbage plants (Brassica oleracea) which have been of approximately 10 30 cm, are sprayedwith theprepheavily infested with peach aphids (Myzns persicae) are aration of the given active compound until dripping, wet, sprayed with the'prepa'r'ation .of the given active com- These bean plants are heavily infested with spider'mnitefi pound until dripping wet. (Ietrm ychus telarius) in all stages. of deye19pment. .,u

After the specified period of time, the-degree of destruc- After the specified tperiod of time the -effe etiveness tion is determined-as a percentage: -100% means that all of the given active compound preparationi s determined the aphids are ldlled whereasr0% means that none of the by counting the dead mites. The degree of destruction aphids are killed. thus obtained is expressed as a percentage. 100% means Th particular a tiv com o d ht sted, their concenthat all the spider mites are killed whereas 0% means that trations, the evaluation time and the results obtained can none of thespider mites are killed a. a a W s be seen from the following Table 2: The particular active compounds tested, their concen- TABLE 2 [Myzus test] Concentration Degree of of activ destruction in 7 compound in percent after Active compound percent 24 hours (92)--- Br-CHzCHz-O 0 0.1 100 \II 0.01 9

Br-CH -CH-0 0 0.001 20 \H V /P .S...

CHa-O (13)--- BrCH:-CHz-O 0 0.1 100 i \II V 0.01 20 CHz-S (232)-- 111101 0.1 v Bi'-CHz- CHzO\(") CH;S v .1

B1'CH2CHrCH-O\(") I v GET-S v BrCHzCH2-O O /P--S v CH3-S 102 Br-CHr-CHz-O o I 0.1 100 K \ll (1-01 v (HEB-O 21)-.- er-cmonz o o 0.1 100 Q 1 s at. CBHE-S 4, BI'-CH2CHQ-O\(H) V 0.1 100 CiHrS 13 trations, the evaluation time and the results obtained can be seen from the following Table 3:

TABLE 3 [Tetranychus test] Concentration Degree of active destil'1ctioi1'"""' compound in percent Active compound in percent after 48 hours 05 Bf-CH2CHr-O\(]:]) 0.1 09 GHQ-0 (a) CH: 0. 1 100 BrCH2CHO\() GHQ-0 EXAMPLE 4 Mulberry leaves (Morus alba) are sprayed with this Bombyx test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable'preparation of the particular active compound, 1 part byweight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifienvand the resulting concentrate is diluted with water to the desired final concentration.

TABLE 4 [Bombyx test] Concentration Degree of of active destruction 1 compound in in percent Active compound percent alter 3 days Br-OHa-CH-O o /PS I CHa-S v (161).. CH: 0.1 I 100 0. 01 BrCHzCH-O 0 v CzHr-S (20 CH1 CH0 0. 1

Br- 11- 11-0 0 \ll /PS CHa-S j 3, m-oflvcm tkt y 0.1 I

CHa-S m-om-on-o 0 \ll /P-S 7 Cl CHa-S no-- Br-0H,-OH0 0 7 0.1 100 i \H I 0.01 100 P-s -o1 CIHb-O (111)" v cm 0.1 100 y v 0.01 100 v Br CHz- H- 0.001 40 TABLE 4C0ntlnued Concentration Degree of of active destruction compound in in percent Active compound percent after 3 days Br-CHz-CH:OP (-s) Br- CH;- H1 0 0 II S The following further examples illustrate, without limitation, the process for producing the particular new compounds of the present invention:

EXAMPLE 5 Br-CHa-CHz-O O GH3""S (Ha) 0.5 mol methylsulfuric acid bromide is added, at to C., to a solution of 63 g. (0.5 mol) 2-chlorodioxaphospholane-1,3,2 in 100 ml. chloroform, the solvent is then evaporated oif, and the residue is distilled. The yield is 74 g. (58% of the theory).

The O-(2-bromo-ethyl)-S-methyl-thiolphosphoric acid diester chloride boils at 130 C. under a pressure of 2 mm. Hg.

0 CHa- S 4) 44 g. thiophenol and 41 g. tricthylamine in 100 ml. benzene are added, at to 40 C., to 0.4 mol O-(2- bromo ethyl) S methyl-thiolphosphoric acid diester chloride dissolved in 300 ml. benzene. The mixture is subsequently stirred for three hours, then washed, dried and slightly distilled. The yield of O-(2-bromo-ethyl)-S- methyl-S-phenyl-dithiolphosphoric acid ester is 104 g. (80% of the theory), refractive index n =1.6023.

Analysis.C H BrO PS (molecular weight 327). Calculated (percent): P, 9.5; S, 19.6; Br, 24.6. Found (percent): P, 9.4; S, 19.15; Br, 23.18.

EXAMPLE 6 9 Br-CHz-CH-O CHaS b) Preparation takes place in analogy with Example 5 (a), but with the use of 2-chloro-4-methyl-dioxaphospholane-1,3,2.

The yield is 87% of the theory.

CHaS (1 58 g. 4chloro-thiophenol and 41 g. triethylaniine are added to a solution of 107 g. O-[3-bromopropyl-(2)]-S- methyl-thiolphosphoric acid diester chloride in 500 cc. benzene; the reaction mixture is subsequently stirred for 2 hours, then washed, dried, and slightly distilled under a vacuum produced by a mercury pump.

The yield of O-(1-bromo-prop-2-yl)-S-methyl-S-(4'- chloro-phenyl)-dithiolphosphoric acid ester is 69% of the theory, the refractive index n =1.5931.

AnalyS?-:Q gH13BIclo2PSg (molecular weight Calculated (percent):Cl, 9.75; Br, 21.2; P, 8.3. Found (percent): Cl, 10.10; Br, 20.3; P, 8.3.

EXAMPLE 7 on. on;

CHzS (I10) Preparation takes place in manner analogous with that in Example 5(a), but using 2-chloro-4,S-dimethyldioxaphospho1ane-1,3,2.

Yield: of the theory.

CH: CH;

Br-CH-CH-O Br-CHz-CHr-CH-O 0 CH S (Ha) Preparation is effected in analogy with Example5 (a), but with the use of 2-chloro-4-methyl-1,3,2-dioxaphos phorinane.

Yield: 81% of the theory.

Br-cHoHrcH-o o A mixture of 33 g. thiophenol and 31 g. triethylamine in 100 ml. benzene is added, at 20 to 30 C., to 85 g. O-[4-bromo-buty1-(2)]-S-methyl-thiolphosphoric acid diester chloride in 300 ml. benzene. The reaction mixture is subsequently stirred for 3 hours, then washed, dried and slightly. distilled.

The yield of O-(4-bromo-but-2-yl)-S-methyl-S-phenyldithiophosphoric acid ester is 69% of the theory, the refractive index is n =1.5798.

Analysis.---C H BrO PS (molecular weight 355.). Calculated (percent): S, 18.0; P, 8.7. Found (percent): S, 17.1; P, 9.6.

1 7 EXAMPLE 9 Cl-CH:

BI-CHp orns (IIo) Preparation takes place as in Example 5 (a), but using 2-chloro-4-chloromethyl-1,3,2-dioxaphospholane.

Yield: 87% of the theory.

(b) Al-CH:

CHO O O1H5 S (Hr) Preparation takes place in analogy with Example 5 (a), but using ethylsulfenic acid bromide.

The yield is 89% of the theory.

36 g. 4-chloro-thiopheno1 and 26 g. triethylamine in 100 ml. benzene are added, at 30 to 35 C., to 69 g. O- (2-bromo-ethyl) S ethyl-thiolphosphoric acid diester chloride. The mixture is subsequently stirred for three hours, then washed, dried and slightly distilled.

' Yield: 85% of the theory of O-(2-bromo-ethyl)-S- ethyl-S-(4 chloro-phenyl)-dithiophosphoric acid ester, refractive index n '-=l.5966.

Analysis.C H BrClO PS (molecular weight 376). Calculated (percent): Cl, 9.5; S, 17.0; P, 8.3. Found (percent): Cl, 9.54; S, 17.12; P, 8.36.

EXAMPLE 11 CH3 Br-CHz-(BHF-O Preparation takes place in manner analogous with that of Example (a), but with 2-chloro-ethylsulfenic acid bromide and 2 chloro-4 methyl 1,3,2 dioxaphospholane.

(b) OH:

22 g. thiophenol and 21 g. triethylamine in 100 ml. benzene are added, at 20 to 30 C., to a solution of 63 g. O-[3-bromo-propyl (2)] S (2-chloro-ethyl)thiolphosphoric acid diester chloride in 300 ml. benzene; the reaction mixture is subsequently stirred for 2 hours, then washed, dried and slightly distilled.

The yield of 0-(1 bromo-prop 2-y1)-S-(2'-chloro- (ll-CH -CH -S (182) 18 ethyl)-S-phenyl-dithiolphosphoric acid ester is 77% of the theory, the refractive index n =1.5 836.

Analysis.-C H BrClO PS (molecular weight 390). Calculated (percent): Cl, 9.1; P, 7.95. Found (percent): Cl, 8.44; P, 7.87.

EXAMPLE 12 Preparation takes place in analogy with Examples 5 (a), but with the use of phenylsulfenic acid bromide.

Yield: 88% of the theory.

63 g. O-(2-bromoethyl)-S-phenyl-thiolphosphoric acid diester chloride are dissolved in 300 ml. benzene, and to this solution there is added, at 20 to 25 C., a mixture of 22 g. thiophenol and 21 g. triethylamine in ml. benzene. The reaction mixture is subsequently stirred for 3 hours, then washed, dried and slightly distilled.

The yield of O-(2-bromo-et-hyl)-S,S-diphenyl-dithiolphosphoric acid ester is 75% of the theory, the refractive index n =1.6l40.

Analysis.-C H BrO PS- (molecular weight 389). Calculated (percent): S, 16.5; P, 8.0. Found (percent): S. 17.1; P, 7.6.

EXAMPLE 13 Preparation takes place in analogy with Example 5 (a), but with phenylsulfenic acid bromide and 2-chloro-4- methyl-1,3,2-dioxaphospholane.

Yield: 94% of the theory.

(IIi) 13 g. methanol and 41 g. triethylamine in 100 ml. benzene are added, at 20 to 25 C., to a solution of 132 g. O-[3-bromo-propyl-(2)-S-phenyl-thiophosphoric acid diester chloride in 400 ml. benzene; the reaction mixture is subsequently sirred for 3 hours, then washed, dried and slightly distilled.

The yield of O-(l-bromo-prop-2-yl)-O-methyl-S-phenyl-thiolphosphoric acid ester is 72% of the theory, the refractive indes is n =1.5717.

Analysis.C H BrO PS (molecular weight 325) Calculated (percent): P, 9.55. Found (percent): P, 8.90.

In analogous manner, the following compounds can be prepared:

Yield: 83% of the theory of O-(2-bromo-ethyl)-S- phenyl-S-(4-chloro-phenyl)-dithiophosphoric acid ester, refractive index n =1.6'278.

19 Analysis.-C H BrClO PS (molecular weight 424). Calculated (percent): S, 15.1; P, 7.3. Found (percent): S, 15.9; P, 6.9.

Yield: 85% of the theory of O-(2-bromo-ethyl)-S- phenyl-S-(2'-methyl-phenyl)-dithiolphosphoric acid ester, refractive index n =1.6180.

Analysis.C H BrO PS (molecular Weight 403). Calculated (percent): S, 15.9; P, 7.7. Found (percent): S, 16.8; P, 7.73.

Yield: 73% of the theory of O-(I-bromo-prop-Z-yD-S- phenyl-S-(4'-chloro-phenyl)-dithiolphosphoric acid ester, refractive index n =1.'6342.

Analysis.-C H BrClO PS (molecular Weight 438). Calculated (percent): Cl, 8.1; P, 7.1. Found (percent): Cl, 8.12; P, 6.6.

BlCHzCHgO \II /P-S- o1 CH3-S 3) Yield: 80% of the theory of O-(2-brom0-ethyl)-S- methyl-S-(4-chloro-phenyl)-dithiolphosphoric acid ester, refractive index n =1.6064.

Analysis.--C H BrClO PS (molecular weight 362). Calculated (percent): S, 17.7; P, 8.6. Found (percent): S, 17.4; P, 8.6.

Yield: 75% of the theory of O-(2-bromo-ethyl)-S- methyl-S-(2'-methyl-phenyl) -dithiolphosphoric acid ester, refractive index n =1.5951.

Analysis.C H BrO PS (molecular Weight 341). Calculated (percent): S, 18.8; P, 9.1. Found (percent): S, 18.5; P, 9.2.

CHJS

BI- CH2- 20 Yield: 74% of the theory of O-(1-bromo-prop-2-yl)-S- methyl-S-(4'-methyl-phenyl)-dithiolphosphoric acid ester, refractive index n =1.5823.

Analysis. C H BrO PS (molecular weight 355). Calculated (percent): P, 8.7. Found (percent): 8.98.

CH3 CH3 Br-OH-CH-O 0 I orr s 20, Yield: of the theory of O-(3-bromo-but-2-yl)-S- methyl S phenyl-dithiolphosphoric acid ester, refractive index n =1.5656.

Analysis. C H BrO PS (molecular weight 355). Calculated (percent): P, 8.75. Found (percent): P, 9.5.

CHaS 1) Yield: 82% of the theory of O-(1-bromo-but-3-yl)-S- methyl-S-(4-chloro-phenyl)dithiolphosphoric acid ester, refractive index n -=1.5 829.

Analysis. C H BrClO PS (molecular weight 390). Calculated (percent): P, 7.95. Found (percent): P, 8.56.

Ol-OH:

CHQS (271) Yield: 72% of the theory of O-(l-bromo-3-chloroprop-Z-yl) -S methyl-S- (4-chloro-phenyl) dithiolphosphoric acid ester, refractive index n 1.5993.

Analysis.--C H BrCl O PS (molecular weight 410). Calculated (percent): P, 7.6. Found (percent): P, 7.55.

CzH5S 3) Yield: 86% of the theory of O-(2-bromo-ethyl)-S- ethyl-S-phenyl-dithiolphosphoric acid ester, refractive index n ==1.5880.

Analysis. C H BrO PS (molecular Weight 341). Calculated (percent): S, 18.8; P, 9.1. Found (percent): S, 18.12; P, 9.17.

Cl- CHz-CHzS (192) Yield: 74% of the theory of O-(1-br0mo-prop-2-yl)-S- (2' chloro-ethyl) S (4-chloro-phenyl) dithiolphosphoric acid ester, refractive index n -=1.6000.

Analysis. CnHnBIClzOgPS (HIOICCUlaI' Calculated (percent: Cl, 16.8; S, 15.1; P, 7.3. Found (percent): Cl, 16.74; S, 15.9; P, 6.74.

Yield: of the theory of O-(l-bromo-prop-2-yD-S- ethyl-S-phenyl-dithiolphosphoric acid ester, refractive index n =1.5777.

Br- CH3- 21 An;lysis.-C H BrO PS (molecular weight 355). Calculated"(percent):,S, 18.0;P, 8.75. Found. (percent): S, 17i74; iP, 9.1 6. H

BrCHzOH-O O Yield: 79% of the theory of O-(l-bromo-prop-Z-yDS- n-butyl-S phenyl-dithiolphosphoric acid ester, refractive index n -=1.5670.

Analysis.C H BrO PS (molecular weight 383). Calculated (percent): S, 16.7; P, 8.1. Found (percent): S, 16.55; P, 8.21.

Yields-88% of the theory of O=(1-bromo-prop-2-yl)-S- (2'-ethylmercapto-ethyl) S-phenyl-dithiolphosphoric acid ester, refractive index n =1.5 840.

Analysis.C. H BrO PS (molecular weight 415). Calculated (percent): S, 23.1; P, 7.5. Found (percent): S, 23.3; P, 7.21.

Br- C H2- H- fi -Q can-o (163) Yield: 55% of the theory of O-(l-bromo-prop-Z-yD-O- ethyl-S-phenyLthiolphosphoric acid ester, refractive index Analysis.-C H BrO PS (molecular .Weight 339). Calculated (percent): S, 9.4; P, 9.1. Found (percent): S, 8.96; P, 9.29. 7

Yield: 80% of the theory of O-(1-bromo-prop-2-yl)-O- ethyl-S-(4'-chloro-phenyl)-thiolphosphoric acid ester, refractive index n :1.5576.

Analysis.--Ci H BrClO PS (molecular weight 374). Calculated (percent): Cl, 9.5; P, 8.3. Found (percent): CI, 8.86; P, 8.58.

Br-CHz- Yield: 66% of the theory of O-(2 -bromo-ethyl) '0- cyclohexyl-S-phenyl-thiolphosphoric acid ester, refractive index n =1.5619.

Anqlysis.-C H BrO PS (molecular weight 379). Calculated (percent): P, 8.2. Found (percent): P, 7.4.

Yield: 68% of the theory of O-(2-bromo-ethyl)-O-ethyl- S-(4'-chloro-phenyl)-thiolphosphoric acid ester, refractive index n =1.5560.

Atmlysia-C H BrClO PS (molecular weight 360). Calculated (percent): P, 8.6; Cl, 9.8. Found (percent): P, 8.47; Cl, 9.81.

It will be realized that all of the foregoing compounds contemplated by the present invention possess the desired strong and selective pesticidal, especially fungicidal, bactericidal and arthropodicidal, i.e. insecticidal or acaricidal, properties, with regard to a broad spectrum of activity for combating correspondingly fungi, bacteria, insects and acarids, and that such compounds have not only a very slight toxcity toward warm-blooded creatures, but also a concomitantly low phytotoxicity to higher plants.

As may be used herein, the terms arthropod, arthropodicidal and arthropodicide contemplate specifically both insects and acarids. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidal ly effective amount Which in eifect means an insecticidally or acaridically effective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made Without departing from the spirit and scope of the present invention.

What is claimed is:

1. Bromoalkyl-(di)-thiol-phosphoric acid esters of the formula R1 R2 R5 O l I l IL Br-|- (|3 cl1-01I-sR R2 R1 n R0 S a in which R to R each individually is selected from the group consisting of hydrogen, alkyl of 1-2 carbon atoms, and chloro-substituted alkyl of l-2 carbon atoms; R, is selected from the group consisting of alkyl of 1-4 carbon atoms, chloro-substituted alkyl of 1-2 carbon atoms, phenyl, chlorophenyl, and alkyl-phenyl having 1-4 carbon atoms in the alkyl moiety; R is selected from the group consisting of alkyl of 1-4 carbon atoms, alkylmercaptoalkyl having 1-4 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl moiety, phenyl, chlorophenyl, and alkyl-phenyl having l-4 carbon atoms in the alkyl moiety with the proviso that at least one of R and R is selected from the group consisting of said phenyl, chlorophenyl and alkyl-phenyl.

2. Ester according to claim 1 wherein R is selected from the group consisting of hydrogen and C alkyl; R to R and R are hydrogen; R is selected from the group consisting of hydrogen, C alkyl and chloro-C alkyl; R; is selected from the group consisting of C alkyl, chloro- C alkyl, phenyl, chlorophenyl and C alkylphenyl; R is selected from the group consisting of C alkyl, C alkylmercapto-C alkyl, phenyl, chlorophenyl and C alkyl-phenyl; and n is 0-1; with the proviso that at least one of R and R is selected from the group consisting of said phenyl, chlorophenyl and C alkylphenyl.

3. Ester according to claim 1 wherein R is selected from the group consisting of hydrogen and methyl; R to R and R are hydrogen; R is selected from the group consisting of hydrogen, methyl and chloromethyl; R is CH3S/ 6. Ester according to claim 1 wherein such compound is O (2-bromo-ethyl)-S-ethyl-S-phenyl-dithiolphosphoric acid ester of the formula BlCHz-CHz-O IO CHr-S 7. Ester according to claim 1 wherein such compound is O- (Z-brorno-ethyl -S-methyl-S- (4'-chloro-phenyl) -dithiolphosphoric acid ester of the formula B!CHzCH2-O CH -S 8. Ester according to claim 1 wherein such compound is O-(2-bromo-ethyl)-S-ethyl S (4-chloro-phenyl)-dithiolphosphoric acid ester of the formula BlCHgCHz-O 0 \II CH3S 9. Ester according to claim 1 wherein such compound is O-(Z-bromo-ethyl) S methyl-S-(2'-methyl-phenyl) dithiolphosphoric acid ester of the formula CH3 BI-CHz-CHz-O O ll CHa-S 10. Ester according to claim 1 wherein such compound is O-( l-bromo-prop-Z-yl) S methyl S phenyl-dithiolphosphoric acid ester of the formula Br-CHz /CH-0\fl) CHJS 24 11. Ester according to claim 1 wherein such compound is O-(l-brorno-prop-Z-yl) S methyl S (4'-chlorophenyl)-dithiolphosphoric acid ester of the formula CHaS 12. Ester according to claim 1 wherein such compound is O-(4-bromo-but-2-yl) S methyl S phenyl-dithiolphosphoric acid ester of the formula BrCHzCHz-CHO O i Q CH3-S 13. Ester according to claim 1 wherein such compound is O-( l-bromo-3-chloro-prop-2-yl) ,S methyl S phenyldithiolphosphoric acid ester of the formula CH: S

Br-CHr- 14. Ester according to claim 1 wherein such compound is O-(l-bromo-but-S-yl) S methyl S (4'-chlorophenyl)-dithiolphosphoric acid ester of the formula CH3 oHo\o 15. Ester according to claim 1 wherein such compound is O-(l-b1'0m0-pr0p-2-yl) S isopropyl S phenyl-dithiolphosphoric acid ester of the formula References Cited UNITED STATES PATENTS 3,201,444 8/1965 Schrader 260-964X 3,213,122 10/1965 Schrader 260-964 X CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, Assistant Examiner US. Cl. X.R. 

